CN110350180B - Ternary heterojunction NiO/Ni 2 Preparation method of P/N-C nanosheet composite material and application of P/N-C nanosheet composite material in sodium ion battery - Google Patents
Ternary heterojunction NiO/Ni 2 Preparation method of P/N-C nanosheet composite material and application of P/N-C nanosheet composite material in sodium ion battery Download PDFInfo
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Abstract
The invention discloses a ternary heterojunction NiO/Ni 2 A preparation method of a P/N-C nanosheet composite material and application thereof in a sodium ion battery belong to the technical field of negative electrode materials of sodium ion batteries. The technical scheme provided by the invention has the key points that: adding CTAB and a nickel source into a mixed solution of ethanol and water to form a uniform solution, and carrying out hydrothermal reaction on the uniform solution to obtain beta-Ni (OH) 2 An NSs precursor; mixing beta-Ni (OH) 2 Adding NSs precursor into alkaline buffer solution, adding dopamine hydrochloride to react to obtain beta-Ni (OH) 2 @ PDA NSs intermediate; carrying out heat treatment on the intermediate product under the protection of high-purity nitrogen to obtain NiO @ N-C NSs; the NiO @ N-C NSs and the phosphorus source are reasonably proportioned and thermally treated under the protection of high-purity nitrogen to obtain the ternary heterojunction NiO/Ni 2 P/N-C nanosheet composite material. The ternary heterojunction NiO/Ni prepared by the invention 2 The P/N-C nanosheet composite material shows excellent rate capability and cycle performance when used as a sodium ion battery cathode material.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials of sodium-ion batteries, and particularly relates to ternary heterojunction NiO/Ni 2 A preparation method of a P/N-C nanosheet composite material and application of the P/N-C nanosheet composite material in a sodium-ion battery.
Background
The sodium ion battery attracts people's attention due to the advantages of rich sodium resource, good safety performance, low price and the like, and meanwhile, the sodium element and the lithium element are in the same main group, have similar physical and chemical properties, and have similar charge and discharge mechanisms with the lithium ion battery, so the sodium ion battery is considered to be a secondary battery with great potential for developing new energy and realizing large-scale energy storage. In the sodium ion battery, the research and development of a novel high-performance negative electrode material is an effective strategy for improving the performance of the sodium ion battery. The material suitable for the negative electrode of the sodium-ion battery mainly comprises an embedding material, an alloy material and a conversion material, wherein the alloy material and the conversion material are widely concerned due to higher theoretical specific capacity. Ni-based materials are an important research direction for such materials. Wherein NiO as a negative electrode material has relatively low voltage hysteresis, proper reversible potential, high density and high theoretical specific capacity (718 mA h g) -1 ) Relatively low cost and environmental friendliness. But NiO has poor rate capability and cycle performance due to its low conductivity, and its capacity rapidly decays due to severe aggregation and large volume change between NiO nanoparticles during sodium and sodium delignification. Relatively low theoretical specific capacity of Ni 2 The P has a unique nanosheet structure, so that the volume expansion in the embedding and releasing process can be effectively buffered, and the cycle performance is improved to a certain extent. Meanwhile, the weak Ni-P bonding force enables the reversible performance during the conversion reaction to be better. Thus, niO and Ni were constructed 2 The heterostructure of P can optimize the specific capacity of the sodium-ion battery, and the synergistic effect of the components plays an important role in improving the electrochemical reaction activity and the circulation stability of the sodium storage. Therefore, the rational design of heterostructure nanoparticles as negative electrode materials of sodium ion batteries to improve the rate capability and cycle life of the batteries is an ideal way for people to pursue for a long time.
Disclosure of Invention
The technical problem to be solved by the invention is to provideProvides a ternary heterojunction NiO/Ni with simple process, mild reaction condition and higher reaction efficiency 2 Preparation method of P/N-C nanosheet composite material, and ternary heterojunction NiO/Ni prepared by method 2 When the P/N-C nanosheet composite material is used as a negative electrode material of a sodium ion battery, the P/N-C nanosheet composite material has a higher specific surface area, so that the infiltration of electrolyte to an electrode material is facilitated, sodium ions are more embedded and de-embedded on active substances, the capacity of the sodium ion battery is improved, the structure is stable, the sodium ions are enabled to move rapidly in the charging and discharging process, and the cycling stability of the sodium ion battery is improved.
The invention adopts the following technical scheme to solve the technical problems that the ternary heterojunction NiO/Ni 2 The preparation method of the P/N-C nanosheet composite material is characterized by comprising the following specific steps:
step S1: adding CTAB and a nickel source into a mixed solution of ethanol and water, carrying out ultrasonic stirring to form a uniform solution, transferring the uniform solution into a stainless steel autoclave, and carrying out hydrothermal reaction at 160-200 ℃ for 12 to 36h to obtain beta-Ni (OH) 2 The NSs precursor, wherein the nickel source is one or more of nickel acetate, nickel nitrate, nickel chloride, nickel sulfate or nickel hydroxide;
step S2: the beta-Ni (OH) obtained in the step S1 is added 2 Adding the NSs precursor into an alkaline buffer solution with the pH value of 8.0-9.0, performing ultrasonic stirring to form a uniform solution, and then adding dopamine hydrochloride to react to obtain beta-Ni (OH) 2 @ PDA NSs intermediate;
and step S3: beta-Ni (OH) obtained in step S2 2 Heating the intermediate product of @ PDA NSs to 300-550 ℃ at a heating rate of 1-10 ℃/min for heat treatment for 1-6 h under the protection of high-purity nitrogen, and naturally cooling to room temperature to obtain NiO @ N-C NSs;
and step S4: respectively placing the NiO @ N-C NSs obtained in the step S3 and the phosphorus source in two independent porcelain boats, heating to 200-500 ℃ at the heating rate of 1-20 ℃/min for heat treatment for 1-10 h under the protection of high-purity nitrogen, and naturally cooling to room temperature to obtain the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material comprises one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate or phosphorus chloride.
Further preferably, the alkaline buffer solution in step S2 is one or more of a carbonate/bicarbonate buffer solution, a phosphate/hydrogen phosphate buffer solution, or a tris buffer solution.
More preferably, the feeding molar ratio of the NiO @ N-C NSs to the phosphorus source in the step S4 is 1 to 1.
Further preferably, the ternary heterojunction NiO/Ni 2 NiO in P/N-C NSs composite material accounts for NiO/Ni 2 10 to 80 mass percent of P/N-C NSs and Ni 2 P accounts for NiO/Ni 2 The mass percentage of P/N-C NSs is 10-80%, N-C accounts for NiO/Ni 2 The mass percentage of P/N-C NSs is 5-80%, the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material is prepared by constructing NiO and Ni 2 The heterostructure of P can optimize the specific capacity of the sodium-ion battery, and the synergistic effect of the components plays an important role in improving the electrochemical reaction activity and the circulation stability of the sodium storage.
The ternary heterojunction NiO/Ni of the invention 2 The application of the P/N-C nanosheet composite material in the cathode material of the sodium-ion battery is characterized by comprising the following specific steps: 2.2g of CTAB and 2.4mmol of C 4 H 6 NiO 4 ·4H 2 Adding O into a mixed solution of 60mL of ethanol and 11mL of water; ultrasonically stirring the mixture to form a uniform solution; then transferring the uniform solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene and heating the autoclave at 180 ℃ for reaction for 24 hours; repeatedly washing the precipitate with deionized water by centrifugation, and drying at 80 deg.C for 12 hr to obtain light green beta-Ni (OH) 2 An NSs precursor; taking 600mg beta-Ni (OH) 2 NSs precursor was added to 750mL of 10mmol L -1 Magnetically stirring the solution in the trihydroxymethyl aminomethane buffer solution for 30min at room temperature, then adding 300mg of dopamine hydrochloride, and continuously stirring for 6h; then repeatedly washing the precipitate with ethanol and deionized water by a centrifugal separation method; drying the precipitate at 80 deg.C for 8h to obtain beta-Ni (OH) 2 @ PDA NSs intermediate; heating to 350 ℃ at the heating rate of 3 ℃/min under the protection of high-purity nitrogen to calcine beta-Ni (OH) 2 The intermediate product of @ PDA NSs is cooled to room temperature for 2hObtaining NiO @ N-C NSs; finally NiO @ N-C NSs and NaH 2 PO 2 ·H 2 O in two independent porcelain boats, naH on the upstream side of the furnace 2 PO 2 ·H 2 O porcelain boat and the molar ratio of Ni to P is 1; heating to 350 ℃ at a heating rate of 3 ℃/min under the protection of high-purity nitrogen, calcining for 2h, and naturally cooling to room temperature to obtain the ternary heterojunction NiO/Ni 2 P/N-C NSs composite materials;
the prepared ternary heterojunction NiO/Ni 2 The preparation method comprises the following steps of mixing a P/N-C NSs composite material, carbon black and a binder into slurry according to a mass ratio of 60 4 The solution is used as electrolyte, the solvent in the electrolyte is mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1 -1 Under the current density, the first reversible specific capacity reaches 268mAh g -1 After circulating for 100 circles, the product can still be maintained at 116mAh g -1 The capacity retention rate reaches 43.8 percent, and the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material shows excellent rate performance and cycle performance when used as a negative electrode material of a sodium-ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method is simple, mild in reaction condition and high in reaction efficiency, and shows good application prospect;
2. the polydopamine is adopted to wrap and modify NiO particles, the polydopamine contains rich active groups, and the polydopamine has good affinity to NiO nano sheets, so that a stable coating layer structure can be obtained on the surfaces of the NiO nano sheets, and the conductivity of the material is improved;
3. the ternary heterojunction NiO/Ni synthesized by the invention 2 The P/N-C nanosheet composite material can provide additional charge storage, can effectively relieve large volume change during circulation, and provides abundant interface space for sodium ion transmission and electron migration, so that the diffusion distance of electrons and sodium ions is shortened more effectivelyThe electron transfer rate is accelerated;
4. the invention provides a ternary heterostructure NiO/Ni 2 The P/N-C nanosheet composite material and the improvement of the rate capability and the cycle capability of the sodium-ion battery belong to protection contents.
Drawings
FIG. 1 is a NiO/Ni prepared in example 1 2 XRD pattern of P/N-C NSs composite material;
FIG. 2 is a NiO/Ni prepared in example 1 2 SEM image of P/N-C NSs composite material;
FIG. 3 is NiO/Ni prepared in example 1 2 A multiplying power performance diagram of the P/N-C NSs composite material as a negative electrode material of the sodium-ion battery;
FIG. 4 NiO/Ni prepared in example 1 2 And (3) a cycle performance diagram of the P/N-C NSs composite material as a negative electrode material of the sodium-ion battery.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Example 1
NiO/Ni 2 Preparation of P/N-C NSs composite material
2.2g of CTAB and 2.4mmol of C 4 H 6 NiO 4 ·4H 2 Adding O into a mixed solution of 60mL of ethanol and 11mL of water; ultrasonically stirring the mixture to form a uniform solution; then transferring the uniform solution into a 100mL stainless steel autoclave lined with Polytetrafluoroethylene (PTFE) and heating to react for 24h at 180 ℃; repeatedly washing the precipitate with deionized water by centrifugal separation, and drying at 80 deg.C for 12 hr to collect light green beta-Ni (OH) 2 An NSs precursor; taking 600mg of beta-Ni (OH) 2 NSs precursor was added to 750mL of 10mmol L -1 Magnetically stirring the solution in the trihydroxymethyl aminomethane buffer solution (the pH value is between 8.0 and 9.0) for 30min at room temperature, then adding 300mg of dopamine hydrochloride, and continuously stirring for 6h; then repeatedly washing the precipitate with ethanol and deionized water by a centrifugal separation method; at 80Drying the precipitate at the temperature of 8h to obtain beta-Ni (OH) 2 @ PDA NSs intermediate; heating to 350 ℃ at the heating rate of 3 ℃/min under the protection of high-purity nitrogen to calcine beta-Ni (OH) 2 The intermediate product of @ PDA NSs is cooled to room temperature for 2h, and NiO @ N-C NSs can be obtained; finally NiO @ N-C NSs and NaH 2 PO 2 ·H 2 O in two independent porcelain boats, naH on the upstream side of the furnace 2 PO 2 ·H 2 O porcelain boat and the molar ratio of Ni to P is 1; heating to 350 ℃ at a heating rate of 3 ℃/min under the protection of high-purity nitrogen, calcining for 2h, and naturally cooling to room temperature to obtain the ternary heterojunction NiO/Ni 2 P/N-C NSs composite material.
Example 2
NiO/Ni 2 Preparation of P/N-C NSs composite material
2.2g of CTAB and 2.4mmol of C 4 H 6 NiO 4 ·4H 2 Adding O into a mixed solution of 60mL of ethanol and 11mL of water; ultrasonically stirring the mixture to form a uniform solution; then transferring the uniform solution into a 100mL stainless steel autoclave lined with Polytetrafluoroethylene (PTFE) and heating to react for 24h at 180 ℃; repeatedly washing the precipitate with deionized water by centrifugal separation, and drying at 80 deg.C for 12 hr to collect light green beta-Ni (OH) 2 An NSs precursor; taking 600mg beta-Ni (OH) 2 NSs precursor was added to 750mL of 10mmol L -1 Magnetically stirring the solution in the trihydroxymethyl aminomethane buffer solution (the pH value is 8.0-9.0) for 30min at room temperature, then adding 300mg of dopamine hydrochloride, and continuously stirring for 6h; then repeatedly washing the precipitate with ethanol and deionized water by a centrifugal separation method; drying the precipitate at 80 deg.C for 8h to obtain beta-Ni (OH) 2 The intermediate product of @ PDA NSs; heating to 450 ℃ at the heating rate of 5 ℃/min under the protection of high-purity nitrogen to calcine beta-Ni (OH) 2 The intermediate product of @ PDA NSs is cooled to room temperature for 5h, and NiO @ N-C NSs can be obtained; finally NiO @ N-C NSs and NaH 2 PO 2 ·H 2 O in two independent porcelain boats, naH on the upstream side of the furnace 2 PO 2 ·H 2 O porcelain boat and the molar ratio of Ni to P is 1; heating to 450 deg.C at a heating rate of 5 deg.C/min under the protection of high-purity nitrogenCalcining for 2h, and naturally cooling to room temperature to obtain NiO/Ni 2 P/N-C NSs composite material.
Example 3
NiO/Ni 2 Preparation of P/N-C NSs composite material
2.2g of CTAB and 2.4mmol of C 4 H 6 NiO 4 ·4H 2 O is added into a mixed solution of 60mL ethanol and 11mL water; ultrasonically stirring the mixture to form a uniform solution; then transferring the uniform solution into a 100mL stainless steel autoclave lined with Polytetrafluoroethylene (PTFE) and heating to react for 24h at 180 ℃; repeatedly washing the precipitate with deionized water by centrifugal separation, and drying at 80 deg.C for 12 hr to collect light green beta-Ni (OH) 2 NSs precursor; taking 600mg beta-Ni (OH) 2 NSs precursor was added to 750mL of 10mmol L -1 Magnetically stirring the solution in the trihydroxymethyl aminomethane buffer solution (the pH value is between 8.0 and 9.0) for 30min at room temperature, then adding 300mg of dopamine hydrochloride, and continuously stirring for 6h; then repeatedly washing the precipitate with ethanol and deionized water by a centrifugal separation method; drying the precipitate at 80 deg.C for 8h to obtain beta-Ni (OH) 2 @ PDA NSs intermediate; heating to 350 ℃ at a heating rate of 10 ℃/min under the protection of high-purity nitrogen to calcine beta-Ni (OH) 2 The intermediate product of @ PDA NSs is cooled to room temperature for 8h, and NiO @ N-C NSs can be obtained; finally NiO @ N-C NSs and NaH 2 PO 2 ·H 2 O in two independent porcelain boats, naH on the upstream side of the furnace 2 PO 2 ·H 2 O porcelain boat and the molar ratio of Ni to P is 1; heating to 500 ℃ at a heating rate of 10 ℃/min under the protection of high-purity nitrogen, calcining for 5h, and naturally cooling to room temperature to obtain NiO/Ni 2 P/N-C NSs composite material.
XRD and SEM characterization of the ternary heterojunction NiO/Ni prepared in examples 1-3 2 P/N-C NSs composite material, FIG. 1 is the NiO/Ni ternary heterojunction prepared in example 1 2 The XRD pattern of the P/N-C NSs composite material shows that the components of the synthesized material are mainly NiO (JCPDS 89-7130) and Ni 2 P (JCPDS 89-2742) has no diffraction peak because the resulting carbon has an amorphous structure. FIG. 2 is a ternary system prepared in example 1Heterojunction NiO/Ni 2 Scanning Electron Microscope (SEM) picture of P/N-C NSs composite material, niO/Ni can be found from the picture 2 P/N-C NSs composites are formed from a stack of sheets.
Example 4
Ternary heterojunction NiO/Ni 2 Application of P/N-C NSs composite material in preparation of sodium ion battery cathode material
The ternary heterojunction NiO/Ni prepared in example 1 2 P/N-C NSs composite material, carbon black and binder are mixed to prepare slurry according to a mass ratio of 60 4 The solution (solvent is a mixed solution of ethylene carbonate and dimethyl carbonate in a volume ratio of 1).
And (3) carrying out charge and discharge tests on the assembled sodium ion battery on a LAND charge and discharge tester, wherein the tested charge and discharge interval is 0.005-3V. The rate performance of the assembled sodium ion batteries was tested at charge and discharge rates of 0.05C, 0.1C, 0.2C, 0.4C, 0.8C, 1C, 2C, and 4C.
FIG. 3 shows the NiO/Ni ternary heterojunction obtained in example 1 2 And the P/N-C NSs composite material is used as a rate performance graph of the negative electrode material of the sodium-ion battery. FIG. 4 shows the NiO/Ni ternary heterojunction obtained in example 1 2 And (3) a cycle performance diagram of the P/N-C NSs composite material as a negative electrode material of the sodium-ion battery. As can be seen from the figure, the ternary heterojunction NiO/Ni 2 P/N-C NSs composite material at 200mA g -1 Under the current density, the first reversible specific capacity reaches 268mAh g -1 After circulating for 100 circles, the product can still be maintained at 116mAh g -1 The capacity retention rate reaches 43.8 percent, which shows that the NiO/Ni 2 The P/N-C NSs composite material shows excellent rate performance and cycle performance when used as a negative electrode material of a sodium ion battery.
While the foregoing embodiments have described the general principles, features and advantages of the present invention, it will be understood by those skilled in the art that the present invention is not limited thereto, and that the foregoing embodiments and descriptions are only illustrative of the principles of the present invention, and various changes and modifications can be made without departing from the scope of the principles of the present invention, and these changes and modifications are within the scope of the present invention.
Claims (4)
1. Ternary heterojunction NiO/Ni 2 The application of the P/N-C nanosheet composite material in the cathode material of the sodium-ion battery is characterized in that the ternary heterojunction NiO/Ni 2 The P/N-C nanosheet composite material is prepared by the following method:
step S1: adding CTAB and a nickel source into a mixed solution of ethanol and water, carrying out ultrasonic stirring to form a uniform solution, transferring the uniform solution into a stainless steel autoclave, and carrying out hydrothermal reaction at 160-200 ℃ for 12 to 36h to obtain beta-Ni (OH) 2 The NSs precursor, wherein the nickel source is one or more of nickel acetate, nickel nitrate, nickel chloride, nickel sulfate or nickel hydroxide;
step S2: the beta-Ni (OH) obtained in the step S1 is added 2 Adding the NSs precursor into an alkaline buffer solution with the pH value of 8.0-9.0, performing ultrasonic stirring to form a uniform solution, and then adding dopamine hydrochloride to react to obtain beta-Ni (OH) 2 @ PDA NSs intermediate;
and step S3: the beta-Ni (OH) obtained in the step S2 2 Heating the intermediate product of @ PDA NSs to 300-550 ℃ at a heating rate of 1-10 ℃/min under the protection of high-purity nitrogen, carrying out heat treatment for 1-6 h, and naturally cooling to room temperature to obtain NiO @ N-C NSs;
and step S4: respectively placing the NiO @ N-C NSs obtained in the step S3 and the phosphorus source in two independent porcelain boats, heating to 200-500 ℃ at the heating rate of 1-20 ℃/min for heat treatment for 1-10 h under the protection of high-purity nitrogen, and naturally cooling to room temperature to obtain the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material comprises one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate or phosphorus chloride as a phosphorus source;
the ternary heterojunction NiO/Ni 2 NiO in P/N-C NSs composite material accounts for NiO/Ni 2 10-80% of P/N-C NSs and Ni 2 P accounts for NiO/Ni 2 The mass percentage of P/N-C NSs is 10-80%, N-C accounts for NiO/Ni 2 The mass percentage of P/N-C NSs is 5-80%, the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material is prepared by constructing NiO and Ni 2 The heterostructure of P can optimize the specific capacity of the sodium-ion battery, and the synergistic effect of the components plays an important role in improving the electrochemical reaction activity and the circulation stability of the sodium storage.
2. The application according to claim 1, characterized in that the specific process is: 2.2g of CTAB and 2.4mmol of C 4 H 6 NiO 4 ·4H 2 Adding O into a mixed solution of 60mL of ethanol and 11mL of water; ultrasonically stirring the mixture to form a uniform solution; then transferring the uniform solution into a 100mL stainless steel autoclave lined with polytetrafluoroethylene and heating the autoclave at 180 ℃ for reaction for 24 hours; repeatedly washing the precipitate with deionized water by centrifugal separation, and drying at 80 deg.C for 12 hr to collect light green beta-Ni (OH) 2 NSs precursor; taking 600mg beta-Ni (OH) 2 NSs precursor was added to 750mL of 10mmol L -1 Magnetically stirring the trihydroxymethyl aminomethane buffer solution at room temperature for 30min, adding 300mg dopamine hydrochloride, and continuously stirring for 6h; then repeatedly washing the precipitate with ethanol and deionized water by a centrifugal separation method; drying the precipitate at 80 deg.C for 8h to obtain beta-Ni (OH) 2 @ PDA NSs intermediate; heating to 350 ℃ at the heating rate of 3 ℃/min under the protection of high-purity nitrogen to calcine beta-Ni (OH) 2 The intermediate product of @ PDA NSs is cooled to room temperature for 2h, and NiO @ N-C NSs can be obtained; finally NiO @ N-C NSs and NaH 2 PO 2 ·H 2 O in two independent porcelain boats, naH on the upstream side of the furnace 2 PO 2 ·H 2 O porcelain boat and the molar ratio of Ni to P is 1; heating to 350 ℃ at a heating rate of 3 ℃/min under the protection of high-purity nitrogen, calcining for 2h, and naturally cooling to room temperature to obtain the ternary heterojunction NiO/Ni 2 P/N-C NSs composite materials;
the prepared ternary heterojunction NiO/Ni 2 Mixing a P/N-C NSs composite material, carbon black and a binder into slurry according to a mass ratio of 60,using glass fiber microporous filter membrane as a diaphragm, 1mol/L NaClO 4 The solution is used as electrolyte, the solvent in the electrolyte is mixed solution of ethylene carbonate and dimethyl carbonate with the volume ratio of 1 -1 Under the current density, the first reversible specific capacity reaches 268mAh g -1 After circulating for 100 circles, the product can still be maintained at 116mAh g -1 The capacity retention rate reaches 43.8 percent, and the ternary heterojunction NiO/Ni 2 The P/N-C NSs composite material shows excellent rate performance and cycle performance when used as a negative electrode material of a sodium ion battery.
3. Use according to claim 1, characterized in that: in the step S2, the alkaline buffer solution is one or more of carbonate/bicarbonate buffer solution, phosphate/hydrogen phosphate buffer solution or tris buffer solution.
4. Use according to claim 1, characterized in that: in the step S4, the feeding molar ratio of the NiO @ N-C NSs to the phosphorus source is 1-1.
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| CN112635201A (en) * | 2020-12-12 | 2021-04-09 | 珠海复旦创新研究院 | Flexible all-solid-state asymmetric supercapacitor electrode and preparation method thereof by dividing flexible all-solid-state asymmetric supercapacitor electrode into two parts |
| CN113314715B (en) * | 2021-05-20 | 2022-05-31 | 广州大学 | Nickel sulfide composite material and preparation method and application thereof |
| CN113437277B (en) * | 2021-07-20 | 2022-08-05 | 广东工业大学 | Bi 2 S 3 /NiS 2 @ C negative electrode material, sodium ion battery and preparation method of sodium ion battery |
| CN114921809B (en) * | 2022-04-24 | 2022-12-20 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
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